*4.3. Preparation of CS/PVOH/HNT and CS/PVOH/TO@HNT Films/Coatings*

For the preparation of each film/coating, 100 mL of an aqueous 2% *w*/*v* CS solution activated with 1% *v*/*v* acetic acid was used. In this 100 mL of as-prepared 2% *w*/*v* CS solution with 1% *v*/*v* acetic acid PVOH added to achieve final PVOH nominal content at 30% wt. The obtained mixture was refluxed overnight to solubilize PVOH and to achieve a homogeneous CS/PVOH solution. In this, 100 mL of CS/PVOH mixed solution amounts of TO@HNT hybrid nanostructure was added and homogenized for 5 min at 18,000 rpm to achieve final TO@HNT nominal content 5, 10, and 15 wt.% (see part (3) in Figure 12). For comparison amounts of pure HNT were also added into CS/PVOH mixed solution to achieve final HNT nominal content 5, 10, and 15 wt.%. The as-obtained CS/PVOH/xHNT and CS/PVOH/xTO@HNT (x takes values 5, 10, and 15) homogenized coatings were placed in 11 cm diameter petri dishes and dried at ambient temperature. The obtained films were peeled off and preserved inside PE plastic bags at 25 ◦C and 50% RH before the measurements.

**Figure 12.** Schematic presentation of (**1**) distillation process to produce a rich in thymol fraction from pure thyme oil, (**2**) evaporation/adsorption process to modify pure HNT and develop TO@HNT nanohybrids, (**3**) homogenization process to develop CS/PVOH/TO@HNT gels and (**4**) kiwi fruit dipping/coating process. **Figure 12.** Schematic presentation of (**1**) distillation process to produce a rich in thymol fraction from pure thyme oil, (**2**) evaporation/adsorption process to modify pure HNT and develop TO@HNT nanohybrids, (**3**) homogenization process to develop CS/PVOH/TO@HNT gels and (**4**) kiwi fruit dipping/coating process.

#### *4.3. Preparation of CS/PVOH/HNT and CS/PVOH/TO@HNT Films/Coatings 4.4. Characterization of TO@HNT Hybrid Nanostructure*

For the preparation of each film/coating, 100 mL of an aqueous 2% *w*/*v* CS solution activated with 1% *v*/*v* acetic acid was used. In this 100 mL of as-prepared 2% *w*/*v* CS solution with 1% *v*/*v* acetic acid PVOH added to achieve final PVOH nominal content at 30% wt. The obtained mixture was refluxed overnight to solubilize PVOH and to achieve a homogeneous CS/PVOH solution. In this, 100 mL of CS/PVOH mixed solution amounts of TO@HNT hybrid nanostructure was added and homogenized for 5 min at 18,000 rpm to achieve final TO@HNT nominal content 5, 10, and 15 wt.% (see part (3) in Figure 12). For comparison amounts of pure HNT were also added into CS/PVOH mixed solution to achieve final HNT nominal content 5, 10, and 15 wt.%. The as-obtained CS/PVOH/xHNT and CS/PVOH/xTO@HNT (x takes values 5, 10, and 15) homogenized coatings were placed in 11 cm diameter petri dishes and dried at ambient temperature. The obtained The obtained TO@HNT hybrid nanostructure was characterized with XRD analysis, FTIR spectroscopy, and DSC analysis. For XRD analysis a Brücker D8 advance instrument was employed (Brüker, Analytical Instruments, S.A., Athens, Greece) and the measurements were carried out in the range 2θ = 2–30◦ . For the FTIR spectroscopy measurements, an FT/IR-6000 JASCO Fourier transform spectrometer (JASCO, Interlab, S.A., Athens, Greece) was employed. The FTIR spectra were recorded in the range of 4000–400 cm−<sup>1</sup> and the obtained spectra was was the average of 32 scans at 2 cm−<sup>1</sup> resolution. For the DSC experiments, a DSC214 Polyma Differential Scanning Calorimeter (NETZSCH manufacturer, Selb, Germany) was employed. Samples with an average weight in the range of 1.2–3.3 mg were tested under a nitrogen atmosphere with a heating rate of 10 K/min from 50 to 300 ◦C.

#### films were peeled off and preserved inside PE plastic bags at 25 °C and 50% RH before the measurements. *4.5. XRD Analysis of CS/PVOH/HNT and CS/PVOH/TO@HNT Films*

The prepared CS/PVOH/HNT and CS/PVOH/TO@HNT films were characterized with XRD analysis by using a Brücker D8 advance instrument was employed (Brüker, Analytical Instruments, S.A., Athens, Greece) in the range of 2θ = 2–30◦ .
